JP5289755B2 - Curable composition - Google Patents
Curable composition Download PDFInfo
- Publication number
- JP5289755B2 JP5289755B2 JP2007296566A JP2007296566A JP5289755B2 JP 5289755 B2 JP5289755 B2 JP 5289755B2 JP 2007296566 A JP2007296566 A JP 2007296566A JP 2007296566 A JP2007296566 A JP 2007296566A JP 5289755 B2 JP5289755 B2 JP 5289755B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- curable composition
- amine compound
- amine
- reactive silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 86
- -1 amine compound Chemical class 0.000 claims description 78
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 39
- 150000001412 amines Chemical class 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 22
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 238000007710 freezing Methods 0.000 claims description 11
- 230000008014 freezing Effects 0.000 claims description 11
- 239000002736 nonionic surfactant Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000002245 particle Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 18
- 239000003566 sealing material Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 230000003373 anti-fouling effect Effects 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 239000002689 soil Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000005702 oxyalkylene group Chemical group 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 241000282320 Panthera leo Species 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229920005573 silicon-containing polymer Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000951471 Citrus junos Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000005667 alkyl propylene group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000004590 silicone sealant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 125000004814 1,1-dimethylethylene group Chemical group [H]C([H])([H])C([*:1])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- RDMFEHLCCOQUMH-UHFFFAOYSA-N 2,4'-Diphenyldiamine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1N RDMFEHLCCOQUMH-UHFFFAOYSA-N 0.000 description 1
- XQRUEDXXCQDNOT-UHFFFAOYSA-N 2,5-diaminophenol Chemical compound NC1=CC=C(N)C(O)=C1 XQRUEDXXCQDNOT-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- HOLGXWDGCVTMTB-UHFFFAOYSA-N 2-(2-aminophenyl)aniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1N HOLGXWDGCVTMTB-UHFFFAOYSA-N 0.000 description 1
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- 125000004807 2-methylethylene group Chemical group [H]C([H])([H])C([H])([*:2])C([H])([H])[*:1] 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- ZRJOUVOXPWNFOF-UHFFFAOYSA-N 3-dodecoxypropan-1-amine Chemical compound CCCCCCCCCCCCOCCCN ZRJOUVOXPWNFOF-UHFFFAOYSA-N 0.000 description 1
- AXNUJYHFQHQZBE-UHFFFAOYSA-N 3-methylbenzene-1,2-diamine Chemical compound CC1=CC=CC(N)=C1N AXNUJYHFQHQZBE-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QEIQEORTEYHSJH-UHFFFAOYSA-N Armin Natural products C1=CC(=O)OC2=C(O)C(OCC(CCO)C)=CC=C21 QEIQEORTEYHSJH-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
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- 230000003712 anti-aging effect Effects 0.000 description 1
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- 125000003710 aryl alkyl group Chemical group 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 238000004581 coalescence Methods 0.000 description 1
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- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- JFHKCZFPXJVELF-UHFFFAOYSA-L dibutyltin(2+);2,2-diethylhexanoate Chemical compound CCCC[Sn+2]CCCC.CCCCC(CC)(CC)C([O-])=O.CCCCC(CC)(CC)C([O-])=O JFHKCZFPXJVELF-UHFFFAOYSA-L 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- ATJCASULPHYKHT-UHFFFAOYSA-N hexadecane-1,16-diamine Chemical compound NCCCCCCCCCCCCCCCCN ATJCASULPHYKHT-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011009 synthetic ruby Substances 0.000 description 1
- MSVPBWBOFXVAJF-UHFFFAOYSA-N tetradecane-1,14-diamine Chemical compound NCCCCCCCCCCCCCCN MSVPBWBOFXVAJF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Description
本発明は、防汚性および自浄作用に優れた建物用シーリング材等として適当な硬化性組成物に関する。 The present invention relates to a curable composition suitable as a sealing material for buildings having excellent antifouling properties and self-cleaning action.
各種ポリマー材料をベースとした硬化性組成物は従来知られており、これらはシーリング材として土木、建築または電機等、多岐の用途にわたり使用されている。例えば、変成シリコーン系ポリマーをベースとした硬化性組成物は、建築用シーリング材として、外壁の露出目地等で広く使用されている。 Curable compositions based on various polymer materials are known in the art, and these are used as a sealing material for a wide variety of applications such as civil engineering, construction or electrical machinery. For example, a curable composition based on a modified silicone polymer is widely used as a sealing material for buildings, such as an exposed joint of an outer wall.
変成シリコーン系シーリング材は、他のポリマーをベースにしたシーリング材と比べて耐候性等には優れているが、表面の残留タック（ベタツキ）により、ほこり等の汚れが付着し、特に長期間の屋外暴露において、外観が損なわれる問題がある。特に、近年、防汚性に優れた外壁ボードが開発されてきており、外壁ボードと比較したシーリング材部分の汚れは益々目立つようになってきている。 Modified silicone sealants are superior to other polymer-based sealants in terms of weather resistance, etc., but due to residual tack (stickiness) on the surface, dirt and other dirt can adhere, especially for long periods of time. There is a problem that the appearance is impaired in outdoor exposure. In particular, outer wall boards having excellent antifouling properties have been developed in recent years, and dirt on the sealing material portion as compared with the outer wall boards has become more conspicuous.
表面の残留タック（ベタツキ）を抑制したタイプの変成シリコーン系シーリング材として、変成シリコーン系ポリマーとフッ素系界面活性剤を含有する室温硬化性組成物が開示されている（特許文献１）。しかしながら、このシーリング材は残留タック抑制効果が不十分であり、ほこり等の汚れ付着は防げない。さらに、表面耐候性も不十分であり、長期間の屋外暴露によって表面に多数のクラックが発生し、そのクラックにほこり等が溜まるため、経時的にも汚染を防止することはできない。 A room temperature curable composition containing a modified silicone polymer and a fluorosurfactant is disclosed as a modified silicone sealant of the type that suppresses residual tack (stickiness) on the surface (Patent Document 1). However, this sealing material has an insufficient residual tack suppressing effect, and it cannot prevent the adhesion of dirt such as dust. Furthermore, the surface weather resistance is insufficient, and a large number of cracks are generated on the surface due to long-term outdoor exposure, and dust or the like accumulates in the cracks. Therefore, contamination cannot be prevented over time.
また、硬化物表面に経時的に汚染を発生させることが少ない変成シリコーン系シーリング材として、変成シリコーン系ポリマーと、融点が１０〜２００℃であるアミン化合物、重合度が２〜５であるポリグリセリンの脂肪酸エステルまたは融点が１０〜２００℃である非イオン性界面活性剤を含有する室温硬化性組成物が開示されている（特許文献２）。しかしながら、当該シーリング材の表面汚染防止効果は、近年の防汚性に優れた外壁ボードと比較して十分ではなかった。また、当該シーリング材の表面は、付着した汚れが雨水によって洗い流される自浄機能も備えてはいない。 Further, as a modified silicone sealing material that hardly causes contamination on the surface of the cured product over time, a modified silicone polymer, an amine compound having a melting point of 10 to 200 ° C., and a polyglycerol having a polymerization degree of 2 to 5 A room temperature curable composition containing a fatty acid ester or a nonionic surfactant having a melting point of 10 to 200 ° C. is disclosed (Patent Document 2). However, the surface contamination-preventing effect of the sealing material has not been sufficient as compared with recent outer wall boards having excellent antifouling properties. Further, the surface of the sealing material does not have a self-cleaning function in which attached dirt is washed away by rainwater.
近年、建築物の高耐候性・長寿命化、高意匠性、メンテナンスフリー等の要求が高まり、長期間にわたって防汚機能を持つ防汚性外壁材が提案されていることから、建築用シーリング材においてもそれらの機能を備えることが求められており、汚れによる外観の劣化を長期間にわたって防ぐためには、付着した汚れが降雨によって容易に洗い流されることが好ましい。
本発明は、硬化後に優れた防汚性および自浄作用を持続的に発揮する、すなわち、長期間にわたって汚れが付着しにくく、さらに、降雨によって容易に汚れを洗い流すことができる、高耐候性建築用シーリング材等として適当な硬化性組成物を提供することにある。 The present invention continuously exhibits excellent antifouling property and self-cleaning action after curing, that is, it is difficult for dirt to adhere for a long period of time, and furthermore, it can be easily washed away by rain, for high weather resistant construction The object is to provide a curable composition suitable as a sealing material or the like.
本発明者らは、（Ａ）反応性ケイ素基を有するビニル系重合体を主成分とする硬化性組成物において、（Ｂ）式（１）：
−ＮＨ−Ｒ−ＮＨ２ （１）
〔式中、Ｒは、炭素数１〜５の脂肪族炭化水素基を示す〕
で示される基を有するアミン化合物を含有させることで、上記課題を解決できることを見出し、本発明を完成させるに至った。
すなわち、本発明には、以下のものが含まれる。
〔１〕（Ａ）反応性ケイ素基を有するビニル系重合体と、
（Ｂ）式（１）：
−ＮＨ−Ｒ−ＮＨ２ （１）
〔式中、Ｒは、炭素数１〜５の脂肪族炭化水素基を示す〕
で示される基を有するアミン化合物
とを含んでなる、硬化性組成物。
〔２〕アミン化合物（Ｂ）は、
−ＮＨ−Ｃ３Ｈ６−ＮＨ２
で示される基を有する、上記〔１〕に記載の硬化性組成物。
〔３〕アミン化合物（Ｂ）の含有量は、硬化性組成物全体の０．１重量％〜５重量％である、上記〔１〕または〔２〕に記載の硬化性組成物。
〔４〕さらにアミン化合物（Ｂ）とは異なる（Ｃ）アミン化合物を含んでなる、上記〔１〕〜〔３〕のいずれかに記載の硬化性組成物。
〔５〕アミン化合物（Ｃ）は、凝固点３４℃以下の天然由来のアミン化合物および／または融点３５℃以上のアミン化合物である、上記〔４〕に記載の硬化性組成物。
〔６〕凝固点３４℃以下の天然由来のアミン化合物は、ココアルキルアミンである、上記〔５〕に記載の硬化性組成物。
〔７〕融点３５℃以上のアミン化合物は、固形アミン表面に微粉体が固着された微粉体コーティングアミンである、上記〔５〕または〔６〕に記載の硬化性組成物。
〔８〕反応性ケイ素基を有するビニル系重合体（Ａ）は、反応性ケイ素基を有する（メタ）アクリル系重合体である、上記〔１〕〜〔７〕のいずれかに記載の硬化性組成物。
〔９〕硬化後の水に対する表面接触角は１５°以下である、上記〔１〕〜〔８〕のいずれかに記載の硬化性組成物。
In the curable composition whose main component is (A) a vinyl polymer having a reactive silicon group, the present inventors have (B) Formula (1):
—NH—R—NH 2 (1)
[Wherein R represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms]
It has been found that the above-mentioned problems can be solved by including an amine compound having a group represented by the following, and the present invention has been completed.
That is, the present invention includes the following.
[1] (A) a vinyl polymer having a reactive silicon group;
(B) Formula (1):
—NH—R—NH 2 (1)
[Wherein R represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms]
A curable composition comprising an amine compound having a group represented by the formula:
[2] The amine compound (B) is
—NH—C 3 H 6 —NH 2
The curable composition as described in [1] above, which has a group represented by
[3] The curable composition according to [1] or [2], wherein the content of the amine compound (B) is 0.1% by weight to 5% by weight of the entire curable composition.
[4] The curable composition according to any one of [1] to [3], further comprising (C) an amine compound different from the amine compound (B).
[5] The curable composition according to [4] above, wherein the amine compound (C) is a naturally occurring amine compound having a freezing point of 34 ° C. or lower and / or an amine compound having a melting point of 35 ° C. or higher.
[6] The curable composition according to [5] above, wherein the naturally derived amine compound having a freezing point of 34 ° C. or lower is a cocoalkylamine.
[7] The curable composition according to the above [5] or [6], wherein the amine compound having a melting point of 35 ° C. or higher is a fine powder coating amine in which a fine powder is fixed on the surface of a solid amine.
[8] The curable polymer according to any one of [1] to [7], wherein the vinyl polymer (A) having a reactive silicon group is a (meth) acrylic polymer having a reactive silicon group. Composition.
[9] The curable composition according to any one of the above [1] to [8], wherein the surface contact angle with water after curing is 15 ° or less.
本発明の硬化性組成物は、硬化後に優れた防汚性および自浄作用を持続的に発揮するので、すなわち、長期間にわたって汚れが付着しにくく、さらに、降雨によって容易に汚れを洗い流すことができるので、高耐候性建築用シーリング材等として好適に用いることができる。 Since the curable composition of the present invention continuously exhibits excellent antifouling properties and self-cleaning action after curing, that is, it is difficult for dirt to adhere for a long period of time, and it can be easily washed away by rainfall. Therefore, it can be suitably used as a highly weather-resistant building sealing material or the like.
本発明の硬化性組成物は、反応性ケイ素基を有するビニル系重合体（Ａ）を主成分として含有する。本発明において「反応性ケイ素基を有するビニル系重合体」とは、分子内に１個以上の重合性不飽和基を有するビニル系モノマーの１種または２種以上を重合させて得られるビニル系重合体を主鎖骨格とし、末端もしくは側鎖に反応性ケイ素基を含有する重合体を意味する。このような反応性ケイ素基を有するビニル系重合体（Ａ）は、従来公知の方法で製造することができる。また、本発明の硬化性組成物において、反応性ケイ素基を有するビニル系重合体（Ａ）は、単独で用いてもよく、２種以上を併用してもよい。 The curable composition of the present invention contains a vinyl polymer (A) having a reactive silicon group as a main component. In the present invention, the “vinyl polymer having a reactive silicon group” is a vinyl polymer obtained by polymerizing one or more vinyl monomers having one or more polymerizable unsaturated groups in the molecule. It means a polymer having a polymer as a main chain skeleton and a reactive silicon group at the terminal or side chain. Such a vinyl polymer (A) having a reactive silicon group can be produced by a conventionally known method. Moreover, in the curable composition of this invention, the vinyl polymer (A) which has a reactive silicon group may be used independently, and may use 2 or more types together.
上記反応性ケイ素基を有するビニル系重合体（Ａ）の主鎖を構成するビニル系モノマーとしては、例えば、（メタ）アクリル酸系モノマー、スチレン系モノマー、ケイ素基含有ビニル系モノマー、無水マレイン酸、マレイン酸、マレイン酸エステル、フマル酸、フマル酸エステル、マレイミド系モノマー、ビニルエステル系モノマー、アルケン類等が挙げられる。これらは単独で用いてもよいし、２種以上を共重合させてもよい。 Examples of the vinyl monomer constituting the main chain of the vinyl polymer (A) having a reactive silicon group include (meth) acrylic acid monomers, styrene monomers, silicon group-containing vinyl monomers, and maleic anhydride. Maleic acid, maleic acid ester, fumaric acid, fumaric acid ester, maleimide monomer, vinyl ester monomer, alkenes and the like. These may be used alone or two or more of them may be copolymerized.
上記反応性ケイ素基を有するビニル系重合体（Ａ）における「反応性ケイ素基」とは、ケイ素原子に結合した水酸基または加水分解性基を有し、硬化触媒によって触媒される反応によりシロキサン結合を形成することにより架橋しうる基である。加水分解性基としては、特に限定されず、従来公知の加水分解性基であればよい。具体的には、例えば水素原子、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基等が挙げられる。これらのうちでは、水素原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基が好ましく、加水分解性が穏やかで取り扱いやすいという点からアルコキシ基が特に好ましい。 The “reactive silicon group” in the vinyl polymer (A) having a reactive silicon group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and a siloxane bond is formed by a reaction catalyzed by a curing catalyst. It is a group that can be cross-linked by forming. It does not specifically limit as a hydrolysable group, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.
本発明における反応性ケイ素基を有するビニル系重合体（Ａ）としては、硬化後の物性や耐候性の点で、好ましくは数平均分子量が３０００〜５００００（好ましくは３００００〜５００００）である、反応性ケイ素基を有する（メタ）アクリル系重合体が好ましい。このような反応性ケイ素基を有する（メタ）アクリル系重合体としては、例えば、株式会社（株）カネカ製のＳＡ３１０Ｓ、ＳＡ１１０Ｓ等が挙げられる。 The vinyl polymer (A) having a reactive silicon group in the present invention is preferably a reaction having a number average molecular weight of 3000 to 50000 (preferably 30000 to 50000) in terms of physical properties after curing and weather resistance. (Meth) acrylic polymers having a functional silicon group are preferred. Examples of such a (meth) acrylic polymer having a reactive silicon group include SA310S and SA110S manufactured by Kaneka Corporation.
本発明の硬化性組成物中の反応性ケイ素基を有するビニル系重合体（Ａ）の含有量は、通常、硬化性組成物全体の１０〜５０重量％であり、好ましくは１０〜３０重量％である。 The content of the vinyl polymer (A) having a reactive silicon group in the curable composition of the present invention is usually 10 to 50% by weight, preferably 10 to 30% by weight, based on the entire curable composition. It is.
本発明の硬化性組成物は、上記成分（Ａ）に加えて、反応性ケイ素基を有するオキシアルキレン系重合体（Ｅ）を主成分として含有していてもよい。本発明において「反応性ケイ素基を有するオキシアルキレン系重合体」とは、ポリオキシアルキレンを主鎖骨格とし、かつ末端もしくは側鎖に反応性ケイ素基を有する重合体を意味する。このような反応性ケイ素基を有するオキシアルキレン系重合体（Ｅ）は、従来公知の方法で製造することができる。また、本発明の硬化性組成物において、反応性ケイ素基を有するオキシアルキレン系重合体（Ｅ）は、単独で用いてもよく、２種以上を併用してもよい。なお、反応性ケイ素基を有するオキシアルキレン系重合体（Ｅ）における反応性ケイ素基は、上記成分（Ａ）における反応性ケイ素基と同様のものである。 In addition to the said component (A), the curable composition of this invention may contain the oxyalkylene type polymer (E) which has a reactive silicon group as a main component. In the present invention, the “oxyalkylene polymer having a reactive silicon group” means a polymer having polyoxyalkylene as the main chain skeleton and having a reactive silicon group at the terminal or side chain. Such an oxyalkylene polymer (E) having a reactive silicon group can be produced by a conventionally known method. Moreover, in the curable composition of this invention, the oxyalkylene type polymer (E) which has a reactive silicon group may be used independently, and may use 2 or more types together. The reactive silicon group in the oxyalkylene polymer (E) having a reactive silicon group is the same as the reactive silicon group in the component (A).
上記反応性ケイ素基を有するオキシアルキレン系重合体（Ｅ）としては、例えば、反応性ケイ素基を有するポリプロピレンオキシド、反応性ケイ素基を有するポリエチレンオキシド、反応性ケイ素基を有するプロピレンオキシド−エチレンオキシド共重合体等が挙げられる。なかでも入手が容易である点で、ポリプロピレンオキシドを主鎖骨格とし、かつ末端もしくは側鎖に反応性ケイ素基を有する、好ましくは数平均分子量が８０００〜５００００（好ましくは２００００〜５００００）である、ポリプロピレンオキシド重合体が好ましい。このような反応性ケイ素基を有するポリプロピレンオキシドとしては、例えば、（株）カネカ製のＭＳポリマーシリーズ（「ＭＳポリマーＳ−２０３」等）、ＳＡＸ−２２０、旭硝子（株）製の「エクセスター」（商標登録）シリーズ等が挙げられる。 Examples of the oxyalkylene polymer (E) having a reactive silicon group include polypropylene oxide having a reactive silicon group, polyethylene oxide having a reactive silicon group, and propylene oxide-ethylene oxide copolymer having a reactive silicon group. Examples include coalescence. Of these, polypropylene oxide is the main chain skeleton and has a reactive silicon group at the terminal or side chain, and preferably has a number average molecular weight of 8000 to 50,000 (preferably 20,000 to 50,000). Polypropylene oxide polymers are preferred. Examples of such a polypropylene oxide having a reactive silicon group include MS polymer series (“MS polymer S-203”, etc.) manufactured by Kaneka Co., Ltd., SAX-220, and “Exstar” manufactured by Asahi Glass Co., Ltd. (Trademark registration) series and the like.
本発明の硬化性組成物中の反応性ケイ素基を有するオキシアルキレン系重合体（Ｅ）の含有量は、通常、硬化性組成物全体の１０〜５０重量％であり、好ましくは１０〜３０重量％である。 The content of the oxyalkylene polymer (E) having a reactive silicon group in the curable composition of the present invention is usually 10 to 50% by weight, preferably 10 to 30% by weight of the entire curable composition. %.
また、本発明の硬化性組成物においては、上記成分（Ａ）と成分（Ｅ）との混合物に加え、上記成分（Ａ）と成分（Ｅ）との反応物も使用することができる。上記成分（Ａ）と成分（Ｅ）との混合物または反応物としては、例えば、（株）カネカ製のＭＡ９０３、ＭＳＸ９０８、ＭＳＸ９１１、ＭＳＸ９４３等の、反応性ケイ素基を有するポリオキシアルキレン重合体と反応性ケイ素基を有する（メタ）アクリル系重合体との混合物または反応物が挙げられる。このような混合物または反応物の本発明の硬化性組成物中の含有量は、通常、硬化性組成物全体の１０〜５０重量％であり、好ましくは１０〜３０重量％である。 Moreover, in the curable composition of this invention, in addition to the mixture of the said component (A) and component (E), the reaction material of the said component (A) and component (E) can also be used. As a mixture or a reaction product of the component (A) and the component (E), for example, a reaction with a polyoxyalkylene polymer having a reactive silicon group such as MA903, MSX908, MSX911, MSX943 manufactured by Kaneka Corporation And a mixture or a reaction product with a (meth) acrylic polymer having a functional silicon group. The content of such a mixture or reaction product in the curable composition of the present invention is usually 10 to 50% by weight, preferably 10 to 30% by weight, based on the entire curable composition.
本発明の硬化性組成物は、上記の各成分に加えて、式（１）：
−ＮＨ−Ｒ−ＮＨ２ （１）
〔式中、Ｒは、炭素数１〜５の脂肪族炭化水素基を示す〕
で示される基を有するアミン化合物（Ｂ）を含有する。当該アミン化合物を配合することにより、本発明の硬化性組成物の硬化後の表面は、超親水性になり、降雨による自浄作用に優れたものとなる。
当該アミン化合物（Ｂ）は、その分子中に式（１）で示される基を少なくとも１個有していればよく、２個以上有していてもよい。また、アミン化合物（Ｂ）の分子中に式（１）で示される基が２個以上含まれる場合、当該基は同一でも、異なっていてもよい。
また、当該アミン化合物（Ｂ）は、本発明の硬化性組成物において、単独で用いてもよく、２種以上を併用してもよい。
The curable composition of the present invention has the formula (1):
—NH—R—NH 2 (1)
[Wherein R represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms]
The amine compound (B) which has group shown by these is contained. By compounding the amine compound, the surface after curing of the curable composition of the present invention becomes superhydrophilic and has an excellent self-cleaning effect due to rainfall.
The said amine compound (B) should just have at least 1 group shown by Formula (1) in the molecule | numerator, and may have 2 or more. Further, when two or more groups represented by the formula (1) are contained in the molecule of the amine compound (B), the groups may be the same or different.
Moreover, the said amine compound (B) may be used independently in the curable composition of this invention, and may use 2 or more types together.
上記式（１）においてＲで示される「炭素数１〜５の脂肪族炭化水素基」としては、例えば、炭素数１〜５の直鎖または分岐状のアルキレン基（例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、1-メチルエチレン基、2-メチルエチレン基、1-メチルトリメチレン基、2-メチルトリメチレン基、1,1-ジメチルエチレン基、2-エチルトリメチレンなど）、炭素数２〜５の直鎖または分岐状のアルケニレン基（例えば、ビニレン基、プロペニレン基、ブテニレン基、ペンテニレン基、１−メチルビニレン基、１−メチルプロペニレン基、２−メチルプロペニレン基、１−メチルペンテニレン基、３−メチルペンテニレン基、１−エチルビニレン基、１−エチルプロペニレン基など）、炭素数２〜５の直鎖または分岐状のアルキニレン基（例えば、エチニレン基、１−プロピニレン基、１−ブチニレン基、１−ペンチニレン基、１−ヘキシニレン基、２−ブチニレン基、２−ペンチニレン基、１−メチルエチニレン基、３−メチル−１−プロピニレン基、３−メチル−１−ブチニレン基など）などが挙げられる。これらの基は、本発明の目的が達成される限り、任意の置換基で置換されていてもよい。
なかでも、親水性の効果が高い点から、炭素数１〜５の直鎖または分岐状のアルキレン基（特にトリメチレン基）が好ましい。すなわち、上記式（１）で示される基としては、
−ＮＨ−Ｃ３Ｈ６−ＮＨ２
が好ましい。
Examples of the “aliphatic hydrocarbon group having 1 to 5 carbon atoms” represented by R in the above formula (1) include, for example, a linear or branched alkylene group having 1 to 5 carbon atoms (for example, a methylene group, an ethylene group). , Trimethylene group, tetramethylene group, pentamethylene group, 1-methylethylene group, 2-methylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 2-ethyltrimethyl group Methylene, etc.), linear or branched alkenylene groups having 2 to 5 carbon atoms (for example, vinylene group, propenylene group, butenylene group, pentenylene group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropene group) Nylene group, 1-methylpentenylene group, 3-methylpentenylene group, 1-ethylvinylene group, 1-ethylpropenylene group, etc.), straight chain having 2 to 5 carbon atoms or Branched alkynylene group (for example, ethynylene group, 1-propynylene group, 1-butynylene group, 1-pentynylene group, 1-hexynylene group, 2-butynylene group, 2-pentynylene group, 1-methylethynylene group, 3-methyl- 1-propynylene group, 3-methyl-1-butynylene group, etc.). These groups may be substituted with any substituent as long as the object of the present invention is achieved.
Especially, a C1-C5 linear or branched alkylene group (especially trimethylene group) is preferable from the point with a high hydrophilic effect. That is, as the group represented by the above formula (1),
—NH—C 3 H 6 —NH 2
Is preferred.
上記式（１）で示される基を有するアミン化合物としては、例えば、式（２）
Ｒ１−ＮＨ−Ｒ−ＮＨ２ （２）
〔式中、Ｒは前記と同義であり、Ｒ１は炭素数１〜３０程度の炭化水素基を示す〕
で示されるアミン化合物が挙げられる。
Examples of the amine compound having a group represented by the above formula (1) include, for example, the formula (2)
R 1 —NH—R—NH 2 (2)
[Wherein, R is as defined above, and R 1 represents a hydrocarbon group having about 1 to 30 carbon atoms]
The amine compound shown by these is mentioned.
上記式（２）においてＲ１で示される「炭化水素基」としては、脂肪族炭化水素基、脂環式炭化水素基または芳香族炭化水素基である。ここで、脂肪族炭化水素基とは、脂肪族炭化水素から水素を除いた残基である。その具体例としては、メチル基、エチル基、プロピル基のようなアルキル基；ビニル基、アリル基、メタリル基のようなアルケニル基；エチニル基、プロパルギル基のようなアルキニル基などが挙げられる。
脂環式炭化水素基とは、脂環式炭化水素から水素を除いた残基である。この脂環式炭化水素基は、脂環式炭化水素の脂肪族環から水素を除いた残基であってもよいし、脂肪族鎖を有する脂環式炭化水素の脂肪族鎖から水素を除いた残基であってもよい。その例としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基のようなシクロアルキル基；シクロペンチルメチル基、シクロヘキシルメチル基のようなシクロアルキルアルキル基などが挙げられる。
芳香族炭化水素基とは、芳香族炭化水素から水素を除いた残基である。この芳香族炭化水素基は、芳香族炭化水素の芳香族環から水素を除いた残基であってもよいし、脂肪族を有する芳香族炭化水素の脂肪族鎖から水素を除いた残基であってもよいし、脂肪族環を有する芳香族炭化水素の脂肪族環から水素を除いた残基であってもよい。その具体例としては、フェニル基、トリル基、ナフチル基のようなアリール基；ベンジル基、フェネチル基のようなアラルキル基などが挙げられる。
In the above formula (2), the “hydrocarbon group” represented by R 1 is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. Here, the aliphatic hydrocarbon group is a residue obtained by removing hydrogen from an aliphatic hydrocarbon. Specific examples thereof include alkyl groups such as methyl group, ethyl group, and propyl group; alkenyl groups such as vinyl group, allyl group, and methallyl group; alkynyl groups such as ethynyl group and propargyl group.
An alicyclic hydrocarbon group is a residue obtained by removing hydrogen from an alicyclic hydrocarbon. The alicyclic hydrocarbon group may be a residue obtained by removing hydrogen from the aliphatic ring of the alicyclic hydrocarbon, or remove hydrogen from the aliphatic chain of the alicyclic hydrocarbon having an aliphatic chain. It may be a residue. Examples thereof include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; cycloalkylalkyl groups such as cyclopentylmethyl group and cyclohexylmethyl group.
An aromatic hydrocarbon group is a residue obtained by removing hydrogen from an aromatic hydrocarbon. The aromatic hydrocarbon group may be a residue obtained by removing hydrogen from an aromatic ring of an aromatic hydrocarbon, or a residue obtained by removing hydrogen from an aliphatic chain of an aromatic hydrocarbon having an aliphatic group. It may be a residue obtained by removing hydrogen from an aliphatic ring of an aromatic hydrocarbon having an aliphatic ring. Specific examples thereof include aryl groups such as phenyl group, tolyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group.
上記式（２）で示されるアミン化合物としては、例えば、牛脂アルキルプロピレンジアミン、硬化牛脂アルキルプロピレンジアミン、オレイルプロピレンジアミンなどが挙げられ、具体的には、ライオン（株）製のデュオミンＣＤ（Ｃ８〜１８アルキル−ＮＨ−Ｃ３Ｈ６−ＮＨ２）、デュオミンＴ（Ｃ１４〜１８アルキル−ＮＨ−Ｃ３Ｈ６−ＮＨ２）、デュオミンＨＴ（Ｃ１４〜１８アルキル−ＮＨ−Ｃ３Ｈ６−ＮＨ２）、日本油脂（株）製のニッサンアミンＤＯＢ−Ｒ（Ｃ１８Ｈ３５−ＮＨ−Ｃ３Ｈ６−ＮＨ２；オレイルプロピレンジアミン）などの市販品が挙げられる。 Examples of the amine compound represented by the above formula (2) include beef tallow alkyl propylene diamine, cured beef tallow alkyl propylene diamine, and oleyl propylene diamine. Specifically, Duomine CD (C 8 ) manufactured by Lion Corporation. ~ 18 alkyl -NH-C 3 H 6 -NH 2 ), Duomeen T (C 14 to 18 alkyl -NH-C 3 H 6 -NH 2 ), Duomeen HT (C 14 to 18 alkyl -NH-C 3 H 6 Commercial products such as —NH 2 ) and Nipponamine DOB-R (C 18 H 35 —NH—C 3 H 6 —NH 2 ; oleylpropylenediamine) manufactured by NOF Corporation.
本発明の硬化性組成物中におけるアミン化合物（Ｂ）の含有量は、その物性を低下させずに、硬化後の表面に良好な自浄作用を付与する観点から、硬化性組成物全体の０．１〜５重量％であることが好ましく、０．２〜１．５重量％であることがより好ましい。 The content of the amine compound (B) in the curable composition of the present invention is 0. 0% of the entire curable composition from the viewpoint of imparting a good self-cleaning effect to the surface after curing without reducing its physical properties. It is preferably 1 to 5% by weight, and more preferably 0.2 to 1.5% by weight.
本発明の硬化性組成物は、上記の各成分に加えて、上記（Ｂ）とは異なるアミン化合物（Ｃ）を含有していてもよい。当該アミン化合物を配合することにより、本発明の硬化性組成物の硬化後の表面のタックは抑制されるので、該表面は汚れがさらに付着しにくくなる。
当該アミン化合物（Ｃ）としては、硬化後の表面のタックを抑制して本発明の目的を達成させることができるものであれば特に限定されないが、例えば、凝固点３４℃以下の天然由来のアミン化合物、融点３５℃以上のアミン化合物、およびそれらの混合物が挙げられる。
The curable composition of this invention may contain the amine compound (C) different from said (B) in addition to said each component. By blending the amine compound, tackiness of the surface after curing of the curable composition of the present invention is suppressed, so that the surface is more difficult to adhere to dirt.
The amine compound (C) is not particularly limited as long as the surface tack after curing can be suppressed and the object of the present invention can be achieved. For example, a naturally occurring amine compound having a freezing point of 34 ° C. or lower. , Amine compounds having a melting point of 35 ° C. or higher, and mixtures thereof.
上記凝固点３４℃以下の天然由来のアミン化合物としては、動物や植物等の天然素材から得られる原料（例えば、ココナッツ油（やし油）、パーム核油、パーム油等の天然油脂）から抽出、あるいは合成して得られる凝固点３４℃以下（好ましくは２０℃以下）のアミン化合物が挙げられる。具体的には、例えば、花王株式会社製ファーミン（登録商標）０８Ｄ、２０Ｄ、ＣＳ、ライオン株式会社製アーミンＣＤ、０８Ｄ、１２Ｄ等が挙げられる。これらのアミン化合物は、従来公知の方法にしたがって製造することができる。
なかでも、炭素数が８〜１８のアルキル鎖分布を有するアミン化合物が好ましく、特に、炭素数８のオクチル鎖７％程度、炭素数１０のデシル鎖７％程度、炭素数１２のラウリル鎖５１％程度、炭素数１４のテトラデシル鎖１９％程度、炭素数１６のセチル鎖８％程度、炭素数１８のステアリル鎖２％程度、炭素数１８のオレイル鎖６％程度のアルキル鎖分布を有し、凝固点が約１６℃のココアルキルアミン（ココナットアミンなどとも称されるココナッツ油を原料としたアミン）が好ましい。
本発明の硬化性組成物中の凝固点３４℃以下の天然由来のアミン化合物の含有量は、通常、硬化性組成物全体の０．０５〜１０重量％、好ましくは０．１５〜５重量％である。０．０５重量％未満では、硬化後の表面のタックが十分に抑制されず、防汚性が十分に発揮されない場合があり、また１０重量％を超えると硬化物表面に白化現象が著しく発生し、表面外観上の難点となる傾向にある。
The naturally-occurring amine compound having a freezing point of 34 ° C. or lower is extracted from raw materials obtained from natural materials such as animals and plants (for example, natural fats and oils such as coconut oil (palm oil), palm kernel oil, palm oil), Alternatively, an amine compound having a freezing point of 34 ° C. or lower (preferably 20 ° C. or lower) obtained by synthesis may be used. Specific examples include Farmin (registered trademark) 08D, 20D, CS manufactured by Kao Corporation, and Armin CD, 08D, 12D manufactured by Lion Corporation. These amine compounds can be produced according to a conventionally known method.
Of these, amine compounds having an alkyl chain distribution with 8 to 18 carbon atoms are preferred, and in particular, about 7% octyl chains with 8 carbon atoms, about 7% decyl chains with 10 carbon atoms, 51% lauryl chains with 12 carbon atoms. About 14% tetradecyl chain having 14 carbon atoms, about 8% cetyl chain having 16 carbon atoms, about 2% stearyl chain having 18 carbon atoms, and about 6% oleyl chain having 18 carbon atoms, and freezing point Is preferably about 16 ° C. cocoalkylamine (amine made from coconut oil, also called coconut amine).
The content of the naturally-occurring amine compound having a freezing point of 34 ° C. or lower in the curable composition of the present invention is usually 0.05 to 10% by weight, preferably 0.15 to 5% by weight of the entire curable composition. is there. If it is less than 0.05% by weight, the tackiness of the surface after curing may not be sufficiently suppressed, and the antifouling property may not be sufficiently exhibited. If it exceeds 10% by weight, whitening will occur significantly on the surface of the cured product. , Tend to be a difficult point on the surface appearance.
上記融点３５℃以上のアミン化合物としては、融点３５℃以上（好ましくは５０℃以上）の芳香族または脂肪族に属するアミン化合物等が挙げられ、例えば、４，４’−ジアミノジフェニルメタン、２，４’−ジアミノジフェニルメタン、３，３’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルメタン、２，２’−ジアミノビフェニル、２，４’−ジアミノビフェニル、３，３’−ジアミノビフェニル、２，４−ジアミノフェノール、２，５−ジアミノフェノール、ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、２，３−トルエンジアミン、２，４−トルエンジアミン、２，５−トルエンジアミン、２，６−トルエンジアミン、３，４−トルエンジアミン等の芳香族アミン化合物、１，１２−ドデカンジアミン、１，１０−デカンジアミン、１，８−オクタンジアミン、１，１４−テトラデカンジアミン、１，１６−ヘキサデカンジアミン、ステアリルアミン等の脂肪族アミン化合物等が挙げられる。これらのアミン化合物は、従来公知の方法にしたがって製造することができる。
なかでも、融点が３５℃以上（好ましくは５０℃以上）の固形アミン表面に微粉体が固着された微粉体コーティングアミンを用いることが、その物性を低下させずに、硬化後の表面に良好な防汚性を付与する観点から特に好ましい。
Examples of the amine compound having a melting point of 35 ° C. or higher include aromatic or aliphatic amine compounds having a melting point of 35 ° C. or higher (preferably 50 ° C. or higher). For example, 4,4′-diaminodiphenylmethane, 2,4 '-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diamino Phenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, 2,3-toluenediamine, 2,4-toluenediamine, 2,5-toluenediamine, 2,6-toluenediamine, 3,4 -Aromatic amine compounds such as toluenediamine, 1,12-dodecanediamine, 1,10-decane Examples thereof include aliphatic amine compounds such as diamine, 1,8-octanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, and stearylamine. These amine compounds can be produced according to a conventionally known method.
Among them, it is preferable to use a fine powder coating amine in which a fine powder is fixed to a solid amine surface having a melting point of 35 ° C. or higher (preferably 50 ° C. or higher) without deteriorating its physical properties. It is particularly preferable from the viewpoint of imparting antifouling properties.
上記微粉体コーティングアミンは、融点３５℃以上（好ましくは５０℃以上）および中心粒径２０μｍ以下の固形アミンの表面に、中心粒径２μｍ以下の微粉体を、該固形アミンと微粉体の重量比が１／０．００１〜０．５となるように固着させて、表面の活性アミノ基を被覆したものである。このような微粉体コーティングアミンは、例えば、固形アミンを中心粒径２０μｍ以下に粉砕しつつ、同時にこれに微粉体を加えてその中心粒径２μｍ以下となるように混合粉砕するか；または予め中心粒径２０μｍ以下に微粉砕した固形アミンを、中心粒径２μｍ以下の微粉体と共に、高速衝撃式混合撹拌機、圧縮せん断式混合撹拌機または噴霧乾燥装置を用いて固形アミンの表面に微粉体を固着させることにより製造することができる（特開２０００−１１７０９０号参照）。 The fine powder-coated amine is prepared by applying fine powder having a central particle size of 2 μm or less to the surface of a solid amine having a melting point of 35 ° C. or higher (preferably 50 ° C. or higher) and a central particle size of 20 μm or less. Is fixed so as to be 1 / 0.001 to 0.5, and the active amino group on the surface is coated. Such a fine powder coating amine is obtained by, for example, pulverizing a solid amine to a central particle size of 20 μm or less and simultaneously adding and pulverizing the fine powder to the central particle size of 2 μm or less; Using a high-speed impact mixing stirrer, compression shear mixing stirrer, or spray drying device, the fine powder is pulverized to a particle size of 20 μm or less with a fine powder having a center particle size of 2 μm or less. It can manufacture by making it adhere (refer Unexamined-Japanese-Patent No. 2000-1117090).
上記微粉体コーティングアミンの原料となる固形アミンとしては、上記融点３５℃以上（好ましくは５０℃以上）の芳香族または脂肪族に属するアミン化合物が挙げられる。これらの１種または２種以上の混合物を使用に供してよい。かかる固形アミンは、中心粒径２０μｍ以下、好ましくは３〜１５μｍに調整する。 Examples of the solid amine used as a raw material for the fine powder coating amine include aromatic or aliphatic amine compounds having a melting point of 35 ° C. or higher (preferably 50 ° C. or higher). One or a mixture of two or more of these may be used. The solid amine is adjusted to have a center particle size of 20 μm or less, preferably 3 to 15 μm.
上記微粉体コーティングアミンの原料となる微粉体としては、無機系または有機系の中から任意に使用することができ、たとえば無機系物質として酸化チタン、炭酸カルシウム、クレー、シリカ、ジルコニア、カーボン、アルミナ、タルク等、また有機系物質としてポリ塩化ビニル、ポリアクリル樹脂、ポリスチレン、ポリエチレン等が挙げられ、これらの１種または２種以上の混合物を使用に供する。使用量は、固形アミンと微粉体の重量比が１／０．００１〜０．５、好ましくは１／０．００２〜０．４となるように選定する。 The fine powder used as the raw material of the fine powder coating amine can be arbitrarily used from inorganic or organic materials. For example, titanium oxide, calcium carbonate, clay, silica, zirconia, carbon, alumina as inorganic materials. In addition, polyvinyl chloride, polyacrylic resin, polystyrene, polyethylene and the like are exemplified as talc and the like, and one or a mixture of two or more thereof is used. The amount used is selected so that the weight ratio of solid amine to fine powder is 1 / 0.001 to 0.5, preferably 1 / 0.002 to 0.4.
本発明の硬化性組成物における微粉体コーティングアミンの使用量は、通常、硬化性組成物全体の０．０５〜１０重量部、好ましくは０．１〜５重量部の範囲で選定することが好ましい。０．０５重量部未満では、硬化物表面の防汚性が十分に発揮されないことがあり、また１０重量部を超えると、硬化物表面に白化現象が著しく発生し、表面外観上の難点となる傾向にある。 The amount of fine powder coating amine used in the curable composition of the present invention is usually selected in the range of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight of the entire curable composition. . If it is less than 0.05 part by weight, the antifouling property of the surface of the cured product may not be sufficiently exhibited, and if it exceeds 10 parts by weight, a whitening phenomenon occurs remarkably on the surface of the cured product, resulting in a difficulty in surface appearance. There is a tendency.
また、本発明においては、硬化後の表面に良好な防汚性を付与するために、硬化性組成物中に凝固点が３４℃以下である天然由来のアミン化合物と融点が３５℃以上であるアミン化合物の混合物を使用することも好ましい。この場合、凝固点が３４℃以下である天然由来のアミン化合物と融点が３５℃以上であるアミン化合物の含有比率（重量基準）が１：９〜９：１とすることが、硬化表面の防汚性の観点から好ましい。さらに好ましい含有比率は２：８〜８：２であり、とりわけ３：７〜７：３が好ましい。 In the present invention, in order to give good antifouling property to the surface after curing, a naturally occurring amine compound having a freezing point of 34 ° C. or lower and an amine having a melting point of 35 ° C. or higher in the curable composition. It is also preferred to use a mixture of compounds. In this case, the content ratio (weight basis) of the naturally-derived amine compound having a freezing point of 34 ° C. or lower and the amine compound having a melting point of 35 ° C. or higher is 1: 9 to 9: 1. From the viewpoint of sex. A more preferable content ratio is 2: 8 to 8: 2, and 3: 7 to 7: 3 is particularly preferable.
本発明の硬化性組成物中におけるアミン化合物（Ｃ）の総含有量は、硬化物の物性を低下させずに、硬化物表面に良好な防汚性を付与する観点から、硬化性組成物全体の０．０５〜１０重量％であることが好ましく、０．１〜５重量％であることがより好ましい。 The total content of the amine compound (C) in the curable composition of the present invention is the entire curable composition from the viewpoint of imparting good antifouling properties to the cured product surface without reducing the physical properties of the cured product. It is preferable that it is 0.05 to 10 weight% of this, and it is more preferable that it is 0.1 to 5 weight%.
本発明の硬化性組成物は、上記の各成分に加えて、含フッ素非イオン系界面活性剤（Ｄ）を含有していてもよい。含フッ素非イオン系界面活性剤を配合することにより、本発明の硬化性組成物の硬化後の表面は、さらに超親水性になり、降雨による自浄作用にさらに優れたものとなる。
本発明において「含フッ素非イオン系界面活性剤」とは、疎水基である長鎖アルキル基に配位する水素原子の全て（またはその一部分）がフッ素原子に置換された構造を有するフッ素化合物であって、水に溶解したときにイオン化しない化合物を意味する。このような含フッ素非イオン系界面活性剤（Ｄ）は、従来公知の方法で製造することができる。また、本発明の硬化性組成物において、含フッ素非イオン系界面活性剤（Ｄ）は単独で用いてもよく、２種以上を併用してもよい。
The curable composition of the present invention may contain a fluorine-containing nonionic surfactant (D) in addition to the above components. By blending the fluorine-containing nonionic surfactant, the surface after curing of the curable composition of the present invention becomes more superhydrophilic and further excellent in self-cleaning action due to rainfall.
In the present invention, the “fluorine-containing nonionic surfactant” is a fluorine compound having a structure in which all (or part of) hydrogen atoms coordinated to a long-chain alkyl group which is a hydrophobic group are substituted with fluorine atoms. It means a compound that does not ionize when dissolved in water. Such a fluorine-containing nonionic surfactant (D) can be produced by a conventionally known method. Moreover, in the curable composition of this invention, a fluorine-containing nonionic surfactant (D) may be used independently, and may use 2 or more types together.
本発明における含フッ素非イオン系界面活性剤（Ｄ）としては、ＨＬＢ（Ｈｙｄｒｏｐｈｉｌｅ−Ｌｉｐｏｐｈｉｌｅ Ｂａｌａｎｃｅ）値が２〜１０の範囲（好ましくは５〜１０の範囲）にあるものが好ましい。ＨＬＢ値が上記範囲内である場合、上記自浄作用の持続性が良好に確保される。
なお、本明細書におけるＨＬＢ値は、以下の「川上式」にしたがって求められる値である。
ＨＬＢ＝7＋１１．７ｌｏｇ（親水部の式量の総和／親油部の式量の総和）
As the fluorine-containing nonionic surfactant (D) in the present invention, those having an HLB (Hydrophile-Lipophile Balance) value in the range of 2 to 10 (preferably in the range of 5 to 10) are preferable. When the HLB value is within the above range, the sustainability of the self-cleaning action is ensured satisfactorily.
In addition, the HLB value in this specification is a value calculated | required according to the following "Kawakami formula".
HLB = 7 + 11.7log (sum of formula weight of hydrophilic part / sum of formula weight of lipophilic part)
上記含フッ素非イオン系界面活性剤（Ｄ）としては、例えば、オキシアルキレンの繰り返し単位を有する骨格を有し、かつパーフルオロアルキル基を有する含フッ素化合物等が挙げられる。当該化合物およびそれらの混合物の具体例としては、例えば、サーフロンＳ−３８１、Ｓ−３８３、ＫＨ−４０（セイミケミカル株式会社製）等の市販品が挙げられる。 Examples of the fluorine-containing nonionic surfactant (D) include fluorine-containing compounds having a skeleton having a repeating unit of oxyalkylene and having a perfluoroalkyl group. Specific examples of the compound and a mixture thereof include commercially available products such as Surflon S-381, S-383, and KH-40 (manufactured by Seimi Chemical Co., Ltd.).
本発明の硬化性組成物中における含フッ素非イオン系界面活性剤（Ｄ）の含有量は、その物性を低下させずに、硬化後の表面に良好な自浄作用を付与する観点から、硬化性組成物全体の０．０５〜１０重量％であることが好ましく、０．２〜４重量％であることがより好ましい。 The content of the fluorine-containing nonionic surfactant (D) in the curable composition of the present invention is curable from the viewpoint of imparting a good self-cleaning effect to the surface after curing without reducing its physical properties. It is preferable that it is 0.05 to 10 weight% of the whole composition, and it is more preferable that it is 0.2 to 4 weight%.
本発明に係る硬化性組成物は、上記の各成分に加えて、通常の硬化性組成物において使用される各種の添加剤、例えば、硬化触媒、着色剤、有機溶剤等をさらに含有することができる。これらの添加剤は、単独で用いても、２種以上を併用してもよく、また、これらの硬化性組成物中の含有量は、通常、１．０〜３０．０重量％であり、好ましくは１．０〜１０．０重量％である。 The curable composition according to the present invention may further contain various additives used in ordinary curable compositions, for example, a curing catalyst, a colorant, an organic solvent, and the like, in addition to the above-described components. it can. These additives may be used alone or in combination of two or more, and the content in these curable compositions is usually 1.0 to 30.0% by weight, Preferably it is 1.0-10.0 weight%.
上記硬化触媒としては、例えば、ジオクチル酸錫、ジブチル錫ジラウレート、ジブチル錫ビスアセチルアセトナート、ジブチル錫ジアセテート、ジブチル錫ジエチルヘキサノエート、ジブチル錫ジオクテート、ジブチル錫オキサイド、ジブチル錫ビスエトキシシリケート、ジオクチル錫オキサイド等の錫系触媒やテトライソプロピルチタネート、テトラｎ−ブチルチタネートおよびこれらの部分加水分解縮合物、チタンジイソプロピルビスアセチルアセテート、チタンジイソプロピルビスエチルエチルアセトアセテート等のチタン系触媒等が挙げられる。
上記着色剤としては、例えば、ベンガラ、酸化チタン、カーボンブラック、他の着色顔料、染料等が挙げられる。
上記有機溶剤としては、例えば、トルエン、キシレン、メタノール、エタノール、イソプロピルアルコール、ブタノール、アセトン、メチルエチルケトン、リグロイン、酢酸エチル、テトラヒドロフラン、ｎ−ヘキサン、ヘプタン、イソパラフィン系高沸点溶剤等が挙げられる。
Examples of the curing catalyst include, for example, tin dioctylate, dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin oxide, dibutyltin bisethoxysilicate, dioctyl Examples thereof include tin catalysts such as tin oxide, titanium catalysts such as tetraisopropyl titanate, tetra n-butyl titanate and partial hydrolysis condensates thereof, titanium diisopropyl bisacetyl acetate, titanium diisopropyl bisethyl ethyl acetoacetate, and the like.
Examples of the colorant include bengara, titanium oxide, carbon black, other color pigments, and dyes.
Examples of the organic solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, ligroin, ethyl acetate, tetrahydrofuran, n-hexane, heptane, isoparaffin-based high boiling point solvent, and the like.
本発明の硬化性組成物は、これを特に建築用シーリング材等として用いる場合には、硬化物に意匠性を付与するため、平均粒径が３０〜５００μｍ（より好ましくは７０〜４００μｍ）の粒子を更に含有することが好ましい。このような粒子は無機系および／または有機系の物質から構成されてよく、また、球状（真球、楕円球、扁平球、中空球）、粒状、鎖状または繊維状等の任意の形状のものを使用し得る。その具体例としては、アルミナ、炭化珪素、ジルコニア、窒化珪素、セラミック、合成ルビー、サファイヤ、ガラス、フェノール樹脂、アクリル系樹脂、ポリアクリロニトリル、シリカ、ウレタン樹脂、炭酸カルシウム、珪砂、寒水石等の粒子を挙げることができる。
なかでも、アクリル系樹脂から構成される有機粒子を用いると、硬化剤組成物に耐熱性、耐溶剤性または耐候性を付与し得るとともに、硬化表面に良好な艶消し性、若しくはマット調仕上げ塗装外壁用、ゆず肌仕上げ塗装外壁用または砂岩調塗装外壁用に適した意匠性を付与することができる。このようなアクリル系樹脂粒子は、その耐熱温度が１５０〜３００℃であることが好ましく、そのような粒子は架橋ポリメタクリル酸メチル、ポリアクリロニトリル等のポリマーから構成されることが好ましい。このような架橋アクリル系樹脂粒子の市販品としては、東洋紡（株）製のタフチック（登録商標）ＡＲ６５０ＬＬを例示しうる。
上記無機粒子および有機粒子は、単独で若しくは２種以上を併用して使用でき、硬化性組成物中の含有量は好ましくは０．１〜３０重量％、さらに好ましくは２〜２０重量％である。
The curable composition of the present invention is a particle having an average particle size of 30 to 500 μm (more preferably 70 to 400 μm) in order to impart designability to the cured product, particularly when used as a sealing material for construction. It is preferable to further contain. Such particles may be composed of inorganic and / or organic substances, and have any shape such as spherical (spherical, elliptical, flat, hollow), granular, chain, or fibrous. Things can be used. Specific examples thereof include alumina, silicon carbide, zirconia, silicon nitride, ceramic, synthetic ruby, sapphire, glass, phenolic resin, acrylic resin, polyacrylonitrile, silica, urethane resin, calcium carbonate, silica sand, cryolite, etc. Can be mentioned.
Among them, when organic particles composed of acrylic resin are used, the curing agent composition can be imparted with heat resistance, solvent resistance or weather resistance, and the matte finish or matte finish finish can be applied to the cured surface. Design properties suitable for an outer wall, a yuzu skin finish painted outer wall, or a sandstone-like painted outer wall can be imparted. Such acrylic resin particles preferably have a heat resistant temperature of 150 to 300 ° C., and such particles are preferably composed of polymers such as cross-linked polymethyl methacrylate and polyacrylonitrile. Examples of such commercially available crosslinked acrylic resin particles include Tufic (registered trademark) AR650LL manufactured by Toyobo Co., Ltd.
The inorganic particles and organic particles can be used alone or in combination of two or more, and the content in the curable composition is preferably 0.1 to 30% by weight, more preferably 2 to 20% by weight. .
さらに必要に応じて、本発明の硬化性組成物に、通常の充填剤（重質炭酸カルシウム、脂肪酸処理炭酸カルシウム、ヒュームシリカ、沈降性シリカ、カーボンブラック、タルク、酸化チタン等）、可塑剤（アクリル酸エステル系可塑剤、フタル酸ジエステル類、エポキシ化ヘキサヒドロフタル酸ジエステル類、アルキレンジカルボン酸ジエステル類、アルキルベンゼン類等）、密着剤（エポキシ化合物、シランカップリング剤等）、老化防止剤（ヒンダードフェノール類、メルカプタン類、スルフィド類、ジチオカルボン酸塩類、チオウレア類、チオホスフェイト類、チオアルデヒド類等）、揺変剤（コロイダルシリカ、有機ベントナイト、脂肪酸アマイド、ポリアマイドワックス、水添ひまし油等）、水分保給剤（水、無機塩類の水和物等）、紫外線吸収剤・光安定剤（ベンゾトリアゾール類、ヒンダードアミン類等）、酸化防止剤（ヒンダードフェノール類等）等を適量範囲で配合してよい。 Further, if necessary, the curable composition of the present invention may be added to ordinary fillers (heavy calcium carbonate, fatty acid-treated calcium carbonate, fume silica, precipitated silica, carbon black, talc, titanium oxide, etc.), plasticizer ( Acrylic ester plasticizers, phthalic acid diesters, epoxidized hexahydrophthalic acid diesters, alkylene dicarboxylic acid diesters, alkylbenzenes, etc.), adhesives (epoxy compounds, silane coupling agents, etc.), anti-aging agents (hinders) Dophenols, mercaptans, sulfides, dithiocarboxylates, thioureas, thiophosphates, thioaldehydes, etc., thixotropic agents (colloidal silica, organic bentonite, fatty acid amide, polyamide wax, hydrogenated castor oil, etc.) ), Moisture retention agent (water, hydrates of inorganic salts, etc.) , Ultraviolet absorbers, light stabilizers (benzotriazoles, hindered amines, etc.), it may be blended with an appropriate amount range such as an antioxidant (hindered phenols).
上記成分から構成される本発明の硬化性組成物は、上記配合成分を一括混合した一液型で、あるいは上記ポリマー、飽和および／または不飽和のアルキル鎖分布を有するアミン化合物、粒子等を含有する基材と、硬化触媒、着色剤および微粉体コーティングアミン等を含有するトナー液とする等して構成された二液型で、あるいはさらに着色剤等を別の１成分として分離して構成された三液型として使用してもよい。 The curable composition of the present invention composed of the above components is a one-pack type in which the above-mentioned blending components are mixed together, or contains the above polymer, an amine compound having a saturated and / or unsaturated alkyl chain distribution, particles, and the like. And a two-part type composed of a toner liquid containing a curing catalyst, a colorant, a fine powder coating amine, or the like, or further separated as a separate component from the colorant. Alternatively, it may be used as a three-part type.
本発明の硬化性組成物は、硬化時の温度に影響されずに、好ましくは５〜５０℃の範囲で硬化させることができる。また、本発明の硬化性組成物は、例えば、このような温度条件で硬化させた場合、硬化物の表面の水に対する表面接触角が好ましくは１５°以下、特に好ましくは１０°以下になる。かかる表面接触角であることで、防汚性および自浄作用を十分に発揮することができる。
なお、本明細書において表面接触角は、協和界面科学株式会社製ＣＡ−Ｘ１５０型を使用し、画像処理式３点クリック法で求められる値である。
The curable composition of the present invention can be cured preferably in the range of 5 to 50 ° C. without being affected by the temperature during curing. In addition, when the curable composition of the present invention is cured under such temperature conditions, for example, the surface contact angle with respect to water of the surface of the cured product is preferably 15 ° or less, particularly preferably 10 ° or less. With such a surface contact angle, the antifouling property and the self-cleaning effect can be sufficiently exhibited.
In the present specification, the surface contact angle is a value determined by an image processing type three-point click method using a CA-X150 type manufactured by Kyowa Interface Science Co., Ltd.
本発明の硬化性組成物は、とりわけ建築用シーリング材に適用する場合に有効であり、例えば、マット調仕上げ塗装外壁用、ゆず肌仕上げ塗装外壁用または砂岩調塗装外壁用のシーリング材として好適に使用することができる。本発明の硬化性組成物は、上記建築用シーリング材として以外にも、自動車、電器、土木用のシーリング材や、その他接着剤、塗料、コーティング材、ポッティング材、成形物等に適用することができる。 The curable composition of the present invention is particularly effective when applied to an architectural sealant, and is suitable for use as, for example, a sealant for a matte finish exterior wall, a yuzu skin finish exterior wall, or a sandstone finish exterior wall. Can be used. The curable composition of the present invention can be applied to sealing materials for automobiles, electrical appliances, civil engineering, and other adhesives, paints, coating materials, potting materials, molded products, etc. in addition to the above-mentioned architectural sealing materials. it can.
以下、実施例および比較例を挙げて、本発明をより具体的に説明する。なお、実施例等において、特に明記のない限り、記載された単位は重量を基準とする。
また、各実施例および比較例で得られた硬化性組成物について行った性能試験の評価方法を以下に示す。
〔性能試験の評価方法〕
各硬化性組成物をシーリング材として、約３ｍｍ（深さ）×３０ｍｍ（幅）の溝を設けたフレキシブルボード上に打設し、直ちに下記の試験に付した。
Ａ）水に対する初期接触角の測定
温度２３℃、相対湿度５０％雰囲気下で７日間放置した後、０．０５ｍｌの純水を表面に滴下し、１分後の接触角を接触角計（協和界面科学株式会社製ＣＡ−Ｘ１５０型、画像処理式３点クリック法）を用いて測定した。
Ｂ）水に対する温水浸漬後接触角の測定
Ａ）を５０℃温水中に７日間放置した後、温度２３℃、相対湿度５０％にて１日乾燥後、表面を接触角計にて測定した。次いで、０．０５ｍｌの純水を滴下し、１分後の接触角を測定した。
Ｃ）火山灰試験
温度２３℃、相対湿度５０％雰囲気下で７日間放置した後、火山灰を振りかけ、試験体を２０ｃｍの高さから垂直に床に３回落とし、余分な火山灰を振りおとした後、火山灰が付着している割合を判定した。
Ｄ）火山灰洗浄試験
温度２３℃、相対湿度５０％雰囲気下で７日間放置した後、火山灰を振りかけ、試験体を２０ｃｍの高さから垂直に床に３回落とし、余分な火山灰を振りおとした後、垂直に立てた試験体に霧吹きにて水１００ＣＣを１０〜２０ｃｍの距離から吹きかけ、放置乾燥後火山灰が付着している割合を目視にて判定した。
Ｅ）赤土試験
温度２３℃、相対湿度５０％雰囲気下で７日間放置した後、赤土を振りかけ、試験体を２０ｃｍの高さから垂直に床に３回落とし、余分な赤土を振りおとした後、赤土が付着している割合を判定した。
Ｆ）赤土洗浄試験
温度２３℃、相対湿度５０％雰囲気下で７日間放置した後、赤土を振りかけ、試験体を２０ｃｍの高さから垂直に床に３回落とし、余分な赤土を振りおとした後、垂直に立てた試験体に霧吹きにて水１００ＣＣを１０〜２０ｃｍの距離から吹きかけ、放置乾燥後、赤土が付着している割合を目視にて判定した。
Ｇ）カーボンブラックを用いた洗浄試験
温度２３℃、相対湿度５０％雰囲気下で７日間放置した後、５％カーボンブラックを含有したＤＩＮＰ（ジイソノニルフタレート）を塗布し、垂直に立てた試験体に霧吹きにて水１００ＣＣを１０〜２０ｃｍの距離から吹きかけ、放置乾燥後、色差計（ミノルタ社製ＣＲ−３００）にて試験前後の白色度（Ｌ値）の差を測定した。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In Examples and the like, the units described are based on weight unless otherwise specified.
Moreover, the evaluation method of the performance test done about the curable composition obtained by each Example and the comparative example is shown below.
[Evaluation method of performance test]
Each curable composition was used as a sealing material and placed on a flexible board provided with a groove of about 3 mm (depth) × 30 mm (width) and immediately subjected to the following test.
A) Measurement of initial contact angle with water After standing for 7 days in an atmosphere of 23 ° C. and 50% relative humidity, 0.05 ml of pure water was dropped on the surface, and the contact angle after 1 minute was measured with a contact angle meter (Kyowa) It was measured using Interface Science Co., Ltd. CA-X150 type, image processing type 3 point click method).
B) Measurement of contact angle after immersion in warm water in water A) was left in warm water at 50 ° C. for 7 days, dried at a temperature of 23 ° C. and a relative humidity of 50% for 1 day, and then the surface was measured with a contact angle meter. Subsequently, 0.05 ml of pure water was dropped, and the contact angle after 1 minute was measured.
C) Volcanic ash test After standing for 7 days in an atmosphere at a temperature of 23 ° C and a relative humidity of 50%, sprinkle the volcanic ash, drop the test specimen vertically from the height of 20 cm to the floor three times, and shake off excess volcanic ash. The percentage of volcanic ash attached was determined.
D) Volcanic ash cleaning test After standing for 7 days at a temperature of 23 ° C and a relative humidity of 50%, sprinkle the volcanic ash and drop the test specimen vertically from the height of 20 cm to the floor three times to shake off the extra volcanic ash. Thereafter, 100CC of water was sprayed from a distance of 10 to 20 cm by spraying on a vertically standing test body, and the proportion of volcanic ash adhering to the specimen after standing drying was visually determined.
E) Red soil test After standing for 7 days in an atmosphere at a temperature of 23 ° C and a relative humidity of 50%, sprinkle the red soil, drop the test piece vertically from the height of 20 cm to the floor three times, and shake off the excess red soil. The percentage of red soil attached was determined.
F) Red soil washing test After standing for 7 days at a temperature of 23 ° C and a relative humidity of 50%, sprinkle the red soil, drop the test piece vertically from the height of 20 cm to the floor three times, and shake the excess red soil. Thereafter, 100 CC of water was sprayed from a distance of 10 to 20 cm by spraying on a vertically standing test body, and after standing to dry, the proportion of red soil adhered was visually determined.
G) Cleaning test using carbon black After standing for 7 days in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%, DINP (diisononyl phthalate) containing 5% carbon black was applied and sprayed onto a vertical test specimen. The water 100CC was sprayed from a distance of 10 to 20 cm, and after being left to dry, the difference in whiteness (L value) before and after the test was measured with a color difference meter (CR-300 manufactured by Minolta).
〔参考例：微粉体コーティングアミンの製造〕
微粉体コーティングアミンを、特開２０００−１１７０９０号にしたがって以下のように製造した。
中心粒径約８μｍの１，１２−ドデカンジアミン（融点７１℃）７６．９部と中心粒径約０．０２μｍの超微粒子酸化チタン２３．１部を混合し、高速衝撃式混合撹拌機（日清エンジニアリング（株）製、Ｈｉ−Ｘミキサー）にて複合化処理することにより、中心粒径約８μｍの１，１２−ドデカンジアミンの表面に、中心粒径約０．０２μｍの超微粒子酸化チタンが固着してなる微粉体コーティングアミン１００部を得た。
[Reference Example: Production of fine powder coated amine]
A fine powder coated amine was produced in accordance with JP 2000-117090 as follows.
76.9 parts of 1,12-dodecanediamine (melting point 71 ° C.) with a center particle size of about 8 μm and 23.1 parts of ultrafine titanium oxide with a center particle size of about 0.02 μm were mixed together, and a high-speed impact mixing stirrer By combining with a Kiyo Engineering Co., Ltd. (Hi-X mixer), ultrafine titanium oxide having a center particle size of about 0.02 μm is formed on the surface of 1,12-dodecanediamine having a center particle size of about 8 μm. 100 parts of fine powder-coated amine fixed to be obtained.
〔実施例１〜６および比較例１〜５〕
表１に示す各成分を配合し、遊星式撹拌機を用いて混合することで硬化性組成物を得た。得られた各硬化性組成物について、上記方法を用いて性能評価した。その結果を表１に示す。
[Examples 1-6 and Comparative Examples 1-5]
Each component shown in Table 1 was blended and mixed using a planetary stirrer to obtain a curable composition. About each obtained curable composition, performance evaluation was carried out using the said method. The results are shown in Table 1.
※１ アクリル変成シリコーンポリマーＳＡ３１０Ｓ；反応性ケイ素基を有するビニル系重合体［（株）カネカ製］
※２ デュオミンＣＤ；Ｃ８〜１８アルキル−ＮＨ−Ｃ３Ｈ６−ＮＨ２［ライオン（株）製］
※３ デュオミンＴ；Ｃ１４〜１８アルキル−ＮＨ−Ｃ３Ｈ６−ＮＨ２［ライオン（株）製］
※４ デュオミンＨＴ；Ｃ１４〜１８アルキル−ＮＨ−Ｃ３Ｈ６−ＮＨ２［ライオン（株）製］
※５ ニッサンアミンＤＯＢ−Ｒ；Ｃ１８Ｈ３５−ＮＨ−Ｃ３Ｈ６−ＮＨ２［日本油脂（株）製］
※６ アーミン１８Ｄ；Ｃ１８Ｈ３７−ＮＨ２（ステアリルアミン）［ライオン（株）製］
※７ ジブチルアミノプロピルアミン；（Ｃ４Ｈ９）２−Ｎ−Ｃ３Ｈ６−ＮＨ２［広栄化学（株）製］
※８ ヘキサメチレンジアミン；ＮＨ２−Ｃ６Ｈ１２−ＮＨ２［和光純薬（株）製］
※９ ３−ラウリルオキシプロピルアミン；Ｃ１２Ｈ２５−Ｏ−Ｃ３Ｈ６−ＮＨ２［広栄化学（株）製］
※１０ 脂肪酸処理炭酸カルシウム；カルシーズＰＬＳ−５０５［神島化学工業（株）製］
※１１ アルキルベンゼン；アルケン２００Ｐ［新日本石油化学（株）製］
※１２ アクリル系可塑剤；ＡＲＵＦＯＮ（登録商標）ＵＰ−１０００［東亞合成（株）製］
※１３ ビニルエトキシシラン；サイラエース（登録商標）Ｓ−２２０［チッソ（株）製］
※１４ 微粉体コーティングアミン；参考例で製造したもの
* 1 Acrylic modified silicone polymer SA310S; vinyl polymer having reactive silicon groups [manufactured by Kaneka Corporation]
※ 2 Duomeen CD; C 8 to 18 alkyl -NH-C 3 H 6 -NH 2 [ Lion Co., Ltd.]
* 3 Duomin T; C 14-18 alkyl-NH-C 3 H 6 -NH 2 [manufactured by Lion Corporation]
* 4 Duomine HT; C 14-18 alkyl-NH-C 3 H 6 -NH 2 [manufactured by Lion Corporation]
※ 5 Nissan amine DOB-R; C 18 H 35 -NH-C 3 H 6 -NH 2 [ manufactured by NOF Corporation]
※ 6 Armin 18D; C 18 H 37 -NH 2 ( stearylamine) [Lion Co., Ltd.]
* 7 Dibutylaminopropylamine; (C 4 H 9 ) 2 —N—C 3 H 6 —NH 2 [manufactured by Guangei Chemical Co., Ltd.]
※ 8 hexamethylenediamine; NH 2 -C 6 H 12 -NH 2 [ manufactured by Wako Pure Chemical Industries, Ltd.]
* 9 3-lauryloxypropylamine; C 12 H 25 —O—C 3 H 6 —NH 2 [manufactured by Guangei Chemical Co., Ltd.]
* 10 Fatty acid-treated calcium carbonate; Calsees PLS-505 [manufactured by Kamijima Chemical Co., Ltd.]
* 11 Alkylbenzene; Alkene 200P [Shin Nippon Petrochemical Co., Ltd.]
* 12 Acrylic plasticizer: ARUFON (registered trademark) UP-1000 [manufactured by Toagosei Co., Ltd.]
* 13 Vinylethoxysilane; Silaace (registered trademark) S-220 [manufactured by Chisso Corporation]
* 14 Fine powder coating amine; manufactured in Reference Example
表１から明らかなように、実施例１〜６で得られた本発明の硬化性組成物は、初期および温水浸漬後も水に対する接触角が１５°以下と表面親水性に優れ、火山灰に比べて洗浄がより困難な赤土やカーボンに対しても優れた自浄機能を備えている。 As is apparent from Table 1, the curable compositions of the present invention obtained in Examples 1 to 6 have excellent surface hydrophilicity with a contact angle with water of 15 ° or less even after the initial stage and after immersion in warm water, compared with volcanic ash. It has an excellent self-cleaning function even for red soil and carbon, which are more difficult to clean.
Claims (10)
（Ｂ）式（１）：
−ＮＨ−Ｒ−ＮＨ２ （１）
〔式中、Ｒは、炭素数１〜５の脂肪族炭化水素基を示す〕
で示される基を有するアミン化合物と、
（Ｄ）含フッ素非イオン系界面活性剤
とを含んでなる、硬化性組成物。 (A) a vinyl polymer having a reactive silicon group;
(B) Formula (1):
—NH—R—NH 2 (1)
[Wherein R represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms]
An amine compound having a group represented by:
(D) A curable composition comprising a fluorine-containing nonionic surfactant .
−ＮＨ−Ｃ３Ｈ６−ＮＨ２
で示される基を有する、請求項１に記載の硬化性組成物。 The amine compound (B) is
—NH—C 3 H 6 —NH 2
The curable composition of Claim 1 which has group shown by these.
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| JP4002052B2 (en) * | 2000-07-18 | 2007-10-31 | サンスター技研株式会社 | Moisture curable composition for building sealant |
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